A new benzimidazolium - based chiral fluororeceptor 1 has been designed and synthesized. The open cleft of 1 is found to recognize fumarate selectively over maleate in CH3CN by exhibiting greater change in emission. In comparison, the achiral receptor 2, under similar condition, shows poor selectivity in the recognition of fumarate over maleate. Interaction studies were performed by 1H NMR, fluorescence and UV-vis spectroscopic methods. © 2011 Bentham Science Publishers Ltd.